In this study, four new one-component Type II visible-light-absorbing chalcones (CY6–CY9) that include triphenylamine substitute in one side and dimethylaniline in another side have been prepared and applied for free radical photopolymerization. The position and methoxy-substituted of the triphenylamines demonstrate significant influence on their properties. In addition, the triphenylamine-free one-component Type II photoinitiator (CYP2) was also prepared for comparing. All the new photoinitiators exhibit boarder and red-shifted absorption than did the CYP2 one. The maximum absorption peaks were in the range of 414–425 nm. The photochemical properties of the compounds were studied by the electron spin resonance (ESR), steady-state photolysis techniques, and theoretical calculations. Finally, all the one-component Type II photoinitiators were used to initiated the free radical photopolymerization of trimethylolpropane triacrylate (TMPTA) through a Photo-DSC experiment. Markedly, the double bond conversion efficiency for TMPTA in the presence of CY8 exhibits the highest values (UV for 34 % and LED@405 nm for 33 %) than other analogues (UV for 12–20 % and LED@405 nm for 8–13 %) and control sample (UV for 9 % and LED@405 nm for 9 %) under UV lamp and LED@405 nm irradiation source. This work thus demonstrates a judicious chemical design to fine-tune the photopolymerization character in one-component Type II triphenylamine-functionalized chalcones.